EP0051311B1 - Compositions durcissable pormant une seule phase - Google Patents

Compositions durcissable pormant une seule phase Download PDF

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Publication number
EP0051311B1
EP0051311B1 EP81109480A EP81109480A EP0051311B1 EP 0051311 B1 EP0051311 B1 EP 0051311B1 EP 81109480 A EP81109480 A EP 81109480A EP 81109480 A EP81109480 A EP 81109480A EP 0051311 B1 EP0051311 B1 EP 0051311B1
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EP
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Prior art keywords
composition
epoxy
formula
carbon atoms
epoxycyclohexylmethyl
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EP81109480A
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German (de)
English (en)
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EP0051311A1 (fr
Inventor
Allison Stillwell Burhans
Orson Kirk Spurr, Jr.
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Union Carbide Corp
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used

Definitions

  • This invention is directed to a curable composition of a cycloaliphatic epoxide and a compatible amount of propylene oxide adducts of polyhydroxyalkanes.
  • Cycloaliphatic epoxide resins have inherently good electrical properties. Unmodified cycloaliphatic epoxide resins when cured, however, produce inherently brittle materials. Thus, modifications must be made in the cycloaliphatic epoxide resin systems to decrease their brittleness as well as provide tough systems in order to provide the necessary thermal shock resistance (TSR). Also, resin systems with good electrical properties at elevated temperatures are required in many applications.
  • TSR thermal shock resistance
  • the US-A-31 69 954 describes the use of polycaprolactone polyols as plasticizers for vinyl halide resins.
  • Polycaprolactone polyols are not crosslinkable with vinyl halide resins.
  • DE-B-20 35 620 merely indicates that it is known to employ polyols in order to improve the flexibility of epoxy compositions.
  • Said prior art discloses curable compositions on the basis of polyepoxides in the form of a mixture with a polycarboxylic acid anhydride as curing agent and a linear polymer of a cylic ester with terminal hydroxyl groups, which may contain in the chain, apart from an ether bond, also a sulfo bond or an optionally substituted amino group.
  • curable compositions can moreover contain a curing catalyst, an inorganic filler and a silane coupling agent.
  • curable compositions according to the invention when cast into articles, are characterized by an excellent balance of physical properties, high TSR, high heat distortion temperature and good electrical properties.
  • compositions of this invention are useful in making electrical components such as, for example, outdoor insulation applications and coil and transformer encapsulation.
  • the curable one-phase composition of this invention comprises a cycloaliphatic epoxide having an average of more than 1 vicinal epoxy group per molecule and a polyol being a propylene oxide adduct of polyhydroxyalkanes of the formula wherein R io is an alkyl group of 3 to 10 carbon atoms and n is an integer of from 4 to 25 and having a molecular weight of 1000 to 4000 in amount of 10 to 25 weight percent - based on the total weight of the composition, i.e. compositions which does not form a two phase system with the epoxide.
  • the epoxy groups can be terminal epoxy groups or internal epoxy groups as exemplified by the cycloaliphatic epoxides which are subsequently described.
  • Particularly desirable cycloaliphatic epoxides are the cyclohexane diepoxides, that is epoxides having at least one cyclohexane ring to which is attached at least one vicinal epoxy group.
  • Suitable cycloaliphatic epoxides are the following:
  • R 1 through Rg which can be the same or different are hydrogen or alkyl radicals containing 1 to 9 carbon atoms and preferably containing 1 to 3 carbon atoms as for example methyl, ethyl, n-propyl, n-butyl, n-hexyl, 2-ethylhexyl, n-octyl, and n-nonyl;
  • R is a valence bond or a divalent hydrocarbon radical containing 1 to 9 carbon atoms and preferably containing 4 to 6 carbon atoms as for example, alkylene radicals, such as trimethylene, tetramethylene, pentamethylene, hexamethylene, 2-ethylhexamethylene, octamethylene, nonamethylene; cycloaliphatic radicals, such as 1,4-cyclohexane, 1,3-cyclohexane, and 1,2-cyclohexane.
  • alkylene radicals such as trimethylene, tetramethylene, pentamethylene, hexamethylene, 2-ethylhexamethylene, octamethylene, nonamethylene
  • cycloaliphatic radicals such as 1,4-cyclohexane, 1,3-cyclohexane, and 1,2-cyclohexane.
  • Particularly desirable epoxides falling within the scope of Formula I, are those wherein R 1 through Rg are hydrogen and R is alkylene containing 4 to 6 carbon atoms.
  • R single and double primes which can be the same or different, are monovalent substituents such as hydrogen, halogen, i.e. chlorine, bromine, iodine or fluorine, or monovalent hydrocarbon radicals, or radicals as further defined in US-A-3,318,822.
  • Particularly desirable compounds are those wherein all the R's are hydrogen.
  • Suitable cycloalphatic epoxides are the following:
  • the preferred cycloalphatic epoxides are the following:
  • Epoxides with 6 membered ring structures may also be used, such as diglycidyl esters of phthalic acid, partially hydrogenated phthalic acid or fully hydrogenated phthalic acid. Diglycidyl esters of hexahydrophthalic acids being preferred.
  • Illustrative alkylene oxide adducts of polyhydroxyalkanes include the propylene oxide adducts of glycerol, 1,2,4-trihydroxybutane, 1,2,6-trihydroxyhexane, 1,1,1-trimethylolpropane.
  • the preferred alkylene oxide adducts of polyhydroxyalkanes are of the following formula: wherein R 10 is alkyl, 3 carbon atoms, and n is an integer of from 4 to 25.
  • the adduct constitutes preferably from 10 to 20 weight percent.
  • hardeners are the following:
  • phenolic hardeners are the following polyhydric phenols: catechol, hydroquinone, hydroxyhydroquinone, phloroglucinol, resorcinol and pyrogallol; the di and polynuclear phenols such as the bisphenol is described in US-A-2,506,486 and polyphenylols such as novolac condensates of a phenol and a saturated or unsaturated aldehyde containing an average of from 3 to 20 or more phenylol groups per molecule (cf. T. S. Carswell "Phenoplasts", published in 1947 by Interscience Publishers of New York).
  • polyphenylols derived from a phenol and an unsaturated aldehyde such as acrolein are the triphenylols, pentaphenylols and heptaphenylols described in US-A-2,885,385.
  • the phenols may contain alkyl or aryl ring substituents or halogens, as exemplified by the alkyl resorcinols, the tribromo resorcinol and the diphenols containing alkyl and halogen substituents on the aromatic ring (US ⁇ A ⁇ 2,506,486).
  • the polyhydric phenols can consist of two or more phenols connected by such groups as methylene, alkylene ether, ketone, or sulfone.
  • the connecting groups are further exemplified by the following compounds: bis(p-hydroxyphenyl)ether, bis(p-hydroxyphenyl)ketone, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)dimethyl methane and bis(p-hydroxyphenyl)sulfone.
  • one phenolic hydroxyl group is deemed to react with one epoxy group.
  • polycarboxylic acids of the formula:
  • Suitable acids are phthalic acid, isophthalic acid and terephthalic acid.
  • suitable polybasic acids having at least two carboxylic groups per molecule, can be noted the following: tricarballylic acid and timellitic acid.
  • suitable polybasic acids including polyesters thereof, are described in US-A-2,921,925.
  • Suitable anhydrides are the anhydrides of the acids listed above.
  • one carboxylic group is deemed to react with one epoxy group; with respect to anhydrides, one anhydride group is deemed to react with one epoxy group.
  • Preferred hardeners include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.
  • the hardener such as the anhydride may be reacted with the adduct and this reacted product added to the epoxide.
  • additives can be added to the compositions of this invention as is well known in the epoxy art.
  • additives include the following: catalysts or accelerators, such as amines including (2-hydroxy ethyl)trimethyl ammonium hydroxide (45 percent concentration in methanol, known as choline base, benzyl dimethyl amine, 2-methyl imidazole, metallic compounds, such as stannous octanoate, peroxides or ethylene glycol; modifiers such as dimer acid (made from unsaturated C 18 fatty acids and is a mixture of 3 percent mono basic acids, 75 percent dimer acid and 22 percent trimer acid and sold under the name of Empol 1022 8 by Emery Industries), a carboxyl terminated butadiene acrylonitrile (80-20) random copolymer having a molecular weight of about 3300; fillers such as clay, silica or aluminum trihydride which may be coated with, for example, silanes, which fillers may be added in amounts of up to about
  • compositions of this invention are prepared by simply mixing the epoxide, adduct, hardener and other ingredients at room or higher temperatures in a suitable container.
  • the epoxide and adduct may be mixed in one container and the hardener, catalyst and/or accelerator in another container and these two mixed. This blend is then heated in order to effect its cure.
  • the temperature to which the composition of this invention are heated to effect cure will, of course, vary and depend, in part upon the exact formulations of the composition. Generally, temperatures in the range of 100°C to 200°C are used for a period of time ranging from 1 to 6 h.
  • Choline base (2-hydroxy ethyl)trimethyl ammonium hydroxide, 45 percent concentration in methanol.
  • R propyl having a molecular weight of 6000.
  • the type and amount of epoxide (grams) and type and amount of polyol (grams) as shown in Table I were mixed in a container at about 25°C.
  • the amount (grams) of hexahydrophthalic anhydride and the amount (grams) of choline base as shown in Table I were mixed at about 55°C.
  • the contents of the 2 containers were combined and poured into appropriate molds. The contents of the molds were then heated for 2 hours at 100°C and then for 4 hours at 160°C.
  • the cured composition was then cut into test samples and tested for heat distortion temperature, TSR, tensile strength, elongation, tensile modulus, dielectric constant and dissipation factor. The appearance of the cured composition was noted. An appearance of opacity indicates that a second phase has been formed.
  • the type and amount of epoxide (grams) and type and amount of polyol (grams) as shown in Table II were mixed in a container at about 25°C.
  • the amount (grams) of hexahydrophthalic anhydride and the amount (grams) of choline base as shown in Table II were mixed at about 55°C.
  • the contents of the two containers were combined and poured into appropriate molds. The contents of the molds were then heated for 2 hours at 100°C and then for four hours at 160°C.
  • the cured composition was then cut into test samples and tested for heat distortion temperature, TSR, tensile strength, elongation, tensile modulus, dielectric constant and dissipation factor. The appearance of the cured composition was noted.
  • the cured composition was then cut into test samples and tested for heat distortion temperature, TSR, tensile strength, elongation, tensile modulus, dielectric constant and dissipation factor. The appearance of the cured composition was noted.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (7)

1. Composition durcissable à une seule phase, comprenant un époxyde cycloaliphatique ayant en moyenne plus de 1 groupe époxy vicinal par molécule et 10 à 25% en poids, sur la base du poids total de la composition, d'un polyol constitué par le produit d'addition d'oxyde de propylène et de polyhydroxyalcanes de formule:
Figure imgb0025
dans laquelle R10 est un groupe alkyle de 3 à 10 atomes de carbone et n est un nombre entier de 4 à 25, et ayant un poids moléculaire de 1000 à 4000.
2. Composition suivant la revendication 1, dans laquelle R10 est un groupe propyle.
3. Composition suivant la revendication 1 ou 2, dans laquelle l'époxyde cycloaliphatique répond à la formule:
Figure imgb0026
dans laquelle R1 à Rg, qui peuvent être identiques ou différents, représentent l'hydrogène ou des radicaux alkyle contenant 1 à 9 atomes de carbone; R est une liaison de valence ou un radical hydrocarboné divalent contenant 1 à 9 atomes de carbone.
4. Composition suivant la revendication 1, dans laquelle l'époxyde cycloaliphatique répond à la formule:
Figure imgb0027
dans laquelle R1 à Rg, qui peuvent être identiques ou différents, représentent l'hydrogène ou des radicaux alkyle contenant 1 à 9 atomes de carbone.
5. Composition suivant la revendication 1, dans laquelle l'époxyde cycloaliphatique répond à la formule:
Figure imgb0028
dans laquelle les groupes R, qui peuvent être identiques ou différents, représentent des substituants monovalents ou des radicaux hydrocarbonés monovalents.
6. Composition suivant la revendication 1, dans laquelle l'époxyde cycloaliphatique est le 3,4-époxy- cyclohexane-carboxylate de 3,4-époxycyclohexylméthyle, l'adipate de bis(3,4-époxycyclohexylméthyle) ou le 2-(3,4-époxycyclohexyl-5,5-spiro-3,4-époxy)cyclohexane-métadioxanne ou un mélange d'adipate de bis(3,4-époxycyclohexylméthyle) et de 2-(3,4-époxycyclohexyl-5,5-spiro-3,4-époxy)cyclohexane- métadioxanne.
7. Composition suivant les revendications 1 à 6, dans laquelle le durcisseur est choisi entre des durcisseurs phénoliques ayant au moins deux groupes hydroxyle phénoliques, des acides polybasiques ayant au moins deux groupes acide carboxylique par molécule et des anhydrides de ces acides polybasiques.
EP81109480A 1980-11-03 1981-11-02 Compositions durcissable pormant une seule phase Expired EP0051311B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81109480T ATE28205T1 (de) 1980-11-03 1981-11-02 Haertbare einphasige zusammensetzung.

Applications Claiming Priority (2)

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US20344080A 1980-11-03 1980-11-03
US203440 1980-11-03

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EP0051311A1 EP0051311A1 (fr) 1982-05-12
EP0051311B1 true EP0051311B1 (fr) 1987-07-08

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JP (1) JPS608246B2 (fr)
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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO169450C (no) * 1982-09-30 1992-06-24 Union Carbide Corp Stoepepreparat paa basis av et cykloalifatisk epoksyd
CA1243147A (fr) * 1983-02-07 1988-10-11 Union Carbide Corporation Compositions photocopolymerisables a base de substances organiques epoxydes et hydroxyles, et de derives de substitution de mono-epoxyde cycloaliphatique comme diluants reactifs
CA1240439A (fr) * 1983-02-07 1988-08-09 Union Carbide Corporation Compositions photocopolymerisables a base d'epoxyde et d'un produit organique hydroxyle renfermant des groupements hydroxy primaires
US4567216A (en) * 1983-12-22 1986-01-28 Union Carbide Corporation Thermoplastic modified epoxy compositions
DE3433851C2 (de) * 1984-09-14 1987-01-08 Gurit-Essex Ag, Freienbach Chemisch härtbare Harze aus 1-Oxa-3-aza-tetralin-Gruppen enthaltenden Verbindungen und cycloaliphatischen Epoxid-harzen, Verfahren zu deren Herstellung sowie Verwendung solcher Harze
DE3675063D1 (de) * 1985-04-17 1990-11-29 Union Carbide Corp Mischungen von polycaprolactonpolyolen und polyepoxyden.
JPS6254925U (fr) * 1985-09-24 1987-04-06
EP0221559A3 (fr) * 1985-11-07 1988-09-14 Union Carbide Corporation Compositions photocopolymérisables à base de résines époxydes et produits organiques contenant des groupes hydroxyles
JPS6356103U (fr) * 1986-10-01 1988-04-14
JPH0739464B2 (ja) * 1987-04-22 1995-05-01 ダイセル化学工業株式会社 成形用樹脂型剤
JPH01176050U (fr) * 1988-05-27 1989-12-14
EP0348193A3 (fr) * 1988-06-24 1990-09-12 Somar Corporation Composition de résine époxyde
JP2923229B2 (ja) * 1995-04-24 1999-07-26 株式会社北川鉄工所 生コンクリートの製造用可変速ミキサおよびその製造方法
CN1875045A (zh) * 2003-11-03 2006-12-06 联合碳化化学及塑料技术公司 更韧的脂环族环氧树脂
JP5660778B2 (ja) * 2009-12-22 2015-01-28 日本化薬株式会社 ジオレフィン化合物、エポキシ化合物、及び該組成物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3169945A (en) * 1956-04-13 1965-02-16 Union Carbide Corp Lactone polyesters
CH454455A (de) * 1965-04-07 1968-04-15 Ciba Geigy Verfahren zur Herstellung mechanisch beanspruchter Konstruktionselemente aus glasfaserverstärkten härtbaren Epoxydharzmassen
DE2035620B2 (de) * 1969-07-17 1976-06-10 Union Carbide Corp., New York, N.Y. (V.StA.) Haertbare zusammensetzung auf basis von polyepoxid und einem linearen polymerisat eines esters mit endstaendigen hydroxylgruppen

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DE3176297D1 (en) 1987-08-13
JPS608246B2 (ja) 1985-03-01
JPS57105420A (en) 1982-06-30
ATE28205T1 (de) 1987-07-15
EP0051311A1 (fr) 1982-05-12

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